KR100800984B1 - Dyeing or printing method of manufactured natural polymer and hydrophobic synthetic fiber material - Google Patents

Abstract

The present invention is a method for dyeing or printing a manufactured natural polymer or hydrophobic synthetic fibrous material, characterized by using a dye of formula (1), tricolor dyeing of the produced natural polymer or hydrophobic synthetic fibrous material and mass dyeing of plastic material The use of these dyes and methods for producing combinations of tone-in-tone dyed plastic materials and natural polymers or synthetic fiber materials produced.

Formula 1

In Formula 1 above,

R ₁ is hydrogen, hydroxyl or radical —NHCO—R ₆ , wherein R ₆ is C ₁ -C ₆ alkyl or unsubstituted or C ₁ -C ₄ alkyl- or halogen substituted phenyl,

R ₂ is hydrogen, hydroxyl or radical WR ₇ where W is -NHCO- or -S- and R ₇ is C ₁ -C ₆ alkyl or unsubstituted or C ₁ -C ₄ alkyl- or halogen-substituted phenyl )

R ₃ is hydrogen,

R ₄ is hydrogen or hydroxyl,

R ₅ is hydrogen, halogen, methoxy, phenoxy or phenylthio, or

(여기서, 환 A 및 B는 독립적으로 추가의 치환체를 가질 수 있다)을 형성한다.R ₃ and R ₄ combine to form a radical

Wherein Rings A and B may independently have additional substituents.

Dyeing, Printing, Hydrophobic Synthetic Fiber Materials, Natural Polymers

Description

A process for dyeing or printing manufactured natural polymer and synthetic hydrophobic fiber materials}

The present invention relates to a method for dyeing or printing a produced natural polymer or hydrophobic synthetic fibrous material.

Dyes useful for dyeing or printing natural polymers or hydrophobic synthetic fibrous materials produced, in particular disperse dyes, ie dyes without water-soluble groups, are well known.

However, it has been found that the dyeings or printings obtained with these dyes do not always fully meet the highest requirements, especially with regard to hot light fastness. Therefore, there is a need for a new method for producing dyeings or printings having thermoluminescent fastnesses with good general fastnesses.

It has now been surprisingly found that the dyeings or printings obtained by the process of the present invention substantially meet the standard conditions indicated below.

Accordingly, the present invention provides a method for dyeing or printing a manufactured natural polymer or hydrophobic synthetic fibrous material, using a dye of formula (1).

In Formula 4 above,

R ₁ is hydrogen, hydroxyl or radical —NHCO—R ₆ , wherein R ₆ is C ₁ -C ₆ alkyl or unsubstituted or C ₁ -C ₄ alkyl- or halogen substituted phenyl,

R ₂ is hydrogen, hydroxyl or radical WR ₇ where W is -NHCO- or -S- and R ₇ is C ₁ -C ₆ alkyl or unsubstituted or C ₁ -C ₄ alkyl- or halogen-substituted phenyl )

R ₃ is hydrogen,

R ₄ is hydrogen or hydroxyl,

R ₅ is hydrogen, halogen, methoxy, phenoxy or phenylthio, or

의 라디칼(여기서, 환 A 및 B는 독립적으로 추가의 치환체를 가질 수 있다)을 형성한다.R ₃ and R ₄ in combination

To form radicals wherein rings A and B may independently have additional substituents.

Any substituent useful for rings A and B includes, in particular, halogen, C ₁ -C ₄ alkyl and C ₁ -C ₄ alkoxy. They may be present one or more times.

C ₁ -C ₆ alkyl R ₆ and R ₇ are for example methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, secondary-butyl, tert-butyl, amyl, tert-amyl (1 , 1-dimethylpropyl), 1,1,3,3-tetramethylbutyl, neopentyl, hexyl, 1-methylpentyl, cyclopentyl, cyclohexyl and isomers associated therewith.

Substituents on phenyl or C ₁ -C ₄ alkyl as substituents on rings A and B are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, secondary-butyl and tert-butyl.

C ₁ -C ₄ alkoxy as substituents on rings A and B are, for example, methoxy, ethoxy, propoxy and butoxy.

Halogen is bromine, iodine, especially chlorine.

C ₁ -C ₆ thioalkyl WR ₇ is, for example, methylthio, ethylthio, propylthio or butylthio.

Of the dyes of formula 1, the blue dyes of formulas 2 to 6 are preferred.

Among the dyes of the formula (1), red dyes of the formulas (7) to (10) are also preferred.

Particular preference is given to dyes of formulas (2) and (7).

The dyes used according to the invention are known or can be prepared by known methods.

The dyes of formula 7 are novel and form part of the main subject of the invention.             

Dyes of formula (7) can be prepared analogously to known compounds by known methods.

The dye of formula (7) is obtained by, for example, ring closing the compound of formula (50) in oleum / chlorosulfonic acid and reacting the intermediate of formula (51) with the compound of formula (CH ₃ ) _2- CH-COCl.

Compounds of formula 50 are known and can be prepared by known methods.

The dyes of formula 1 are useful for dyeing and printing natural polymers produced and in particular hydrophobic synthetic fibrous materials, in particular textiles.

Fabrics constituting the blended fabric, including such manufactured natural polymer or hydrophobic synthetic fibrous material, can also be dyed or printed with the dye of the present invention.

Useful manufactured natural polymer fabrics are, in particular, cellulose acetate and cellulose triacetate.

Hydrophobic synthetic fabrics are, in particular, polyesters formed from linear aromatic polyesters such as terephthalic acid and glycols (especially ethylene glycol), or condensation products of terephthalic acid with 1,4-bis (hydroxymethyl) -cyclohexane; Polycarbonates such as polycarbonates formed from α, α-dimethyl-4,4'-dihydroxydiphenylmethane and phosgene; Or polyvinyl chloride or polyamide based fibers.

The dye of formula 1 used according to the invention is applied to the fabric according to known dyeing processes. For example, polyester fibers are adsorbed and dyed from aqueous dispersions in the presence of conventional anionic or nonionic dispersants in the presence or absence of conventional carriers at temperatures of 80-140 ° C, in particular 120-135 ° C. Cellulose acetate is preferably dyed at 60 to 85 ° C. and cellulose triacetate is dyed at temperatures up to 115 ° C.

The dyes used in accordance with the invention only dye minimally adjacent wool and cotton fabrics, ie exhibit very good wool and cotton retaining properties so that they can be used to excellently dye polyester wool and polyester-cellulose blend fabrics.

The dyes used according to the invention are useful for dyeing and printing processes by thermosol, adsorption and continuous dyeing. Adsorption dyeing is preferred. The liquid ratio depends on the device, the substrate and the make-up form. However, the liquid ratio may be selected within a wide range, for example, in the range of 4: 1 to 100: 1, but is preferably 6: 1 to 25: 1.

The amount that each dye can be used in a dyebath or printing paste varies within wide limits and this depends on the desired color tone. Advantageous amounts are generally from 0.01% to 15% by weight, in particular from 0.1% to 10% by weight, based on fiber weight or printing paste.

The fabrics mentioned can be present in various processing forms, for example as fibers, yarns or webs or as woven or loop forming knits.

It is advantageous to convert the dyes used according to the invention into dye preparations before use. To this end, the dye is pulverized so that its particle size is from 0.01 to 10 μm, preferably the particle size is on average 0.1 to 1 μm. Grinding in the presence of a dispersant may be effective. For example, the anhydrous dye is ground with the dispersant or kneaded with the dispersant in paste form and then dried under reduced pressure or by spray drying. Printing pastes and salt baths can be prepared by adding water using the formulation thus obtained.

Prints are conventional thickeners, for example modified or unmodified natural products, such as alginates, British gums, gum arabic, crystalline gums, citrus soybean flour, tragacanth, carboxymethylcellulose, hydroxyethylcellulose , Starch or synthetic products, for example polyacrylamide, polyacrylic acid or copolymers thereof or polyvinyl alcohol.

The dyes used according to the invention impart uniform blue or red shades to the aforementioned materials (particularly polyester materials) having very good user fastnesses, in particular good sublimation fastness and very good light fastness. The obvious feature is very good wash fastness. An excellent feature of the dye according to the invention is that it is further superior in adsorption and build-up.

The dyes used according to the invention are also useful for producing combination shades with another dye or with a yellow dye suitable for trichromatic dyeing.

The present invention further provides a prepared natural polymer or hydrophobic synthetic fibrous material, preferably a polyester fabric, which is dyed or printed by the above-described method.

The present invention further provides natural polymers prepared, in particular hydrophobic synthesis, characterized by the use of at least one blue dye of formulas 2-6 with at least one red dye of formulas 7-25 and a yellow dye of formula 26 Provided are methods for tricolor dyeing or printing fibers.

The dyes of formulas 11-26 can be prepared analogously to known dyes by known or known methods.

The three colors can be matched by adding appropriately selected yellow or orange, red and blue dye dyes as color mixtures whereby the desired hue of the visible spectrum is selected in an appropriate proportion by amount of the dye component.

A preferred embodiment of the tricolor process according to the invention is characterized by the use of a blue dye of formula (2) in combination with a red dye of formula (7) and a yellow dye of formula (26).

A further preferred embodiment of the tricolor process according to the invention is characterized in that the blue dye of formula (2) is used in combination with the red dye of formula (14) and the yellow dye of formula (26).

The present invention further provides a tricolor dye mixture comprising at least one blue dye of formula 2 to 6 together with at least one red dye of formula 7 to 25 and a yellow dye of formula 26.

The method of the present invention for tricolor dyeing or printing can be applied to conventional dyeing and printing processes, respectively. In addition to water and dyes, dyeing solutions or printing pastes may further contain additives, for example wetting agents, antifoams, leveling agents or agents which affect the fabric properties, for example softeners, flame retardants or antifouling agents, water repellents and oil repellents. and also water softeners and natural or synthetic thickeners such as alginates and cellulose ethers.

The process of the invention for tricolor dyeing or printing is also useful for dyeing from insufficient solutions, for example in a continuous dyeing process or in batch and continuous foaming dyeing processes.

Dyeing, in particular dyeing by an adsorption process, is preferred.

Staining is preferably carried out at pH 3 to 7, especially 3 to 5. The liquor ratio can vary within a wide limited range and is for example 5: 1 to 50: 1, preferably 5: 1 to 30: 1. Dyeing is preferably carried out at 100 to 140 ° C, in particular at 120 to 135 ° C.

The tricolor mixture of the present invention is also useful for bulk colored plastics.

The dyes used in the tricolor process of the present invention are notable for their excellent color tone persistence, good fastness and dispersion at various concentrations in tricolor dyeing or printing, in particular very good compatibility and uniform color build-up.

The dyes of the invention and the dyes used according to the invention furthermore have the same color tone and metamerism and the same fastness as the produced natural polymer or hydrophobic synthetic fibrous material in which the mass dyed plastic is printed or dyed from the bath. It is noteworthy that they are suitable for mass coloring of plastics in that they can be used individually as well as in the form of a tricolor mixture.

Thus, the present invention further provides tone-in-tone dyed, which is characterized by mass coloring plastic materials using the same dye of formula 1 and printing or dyeing the produced natural polymer or synthetic fibrous material. A method of producing a combination of a plastic material and a natural polymer or synthetic fibrous material, in particular a textile material, produced.

This combination may consist of plastic parts and upholstery of furniture, for example armchairs or three assembled furniture, or plastic panels or assemblies and seat cover forming parts of an automobile.

Dichroic dyes for the purposes of the present invention have a CIELAB configuration (ΔE ≦ 2.0) (according to the German industry standard DIN 6174).

In order to obtain a dichroic dye by adsorption dyeing, the dye amount must be determined in consideration of the degree of adsorption of the dye, which is usually 80 to 99.9%, generally 90 to 99.9% with respect to the polyester material.

With regard to the natural polymer or synthetic fibrous material produced, the above description and preferred embodiments are also effective.

Plastics useful for bulk dyeing are, for example, dyeable high molecular weight organic materials (polymers) (dielectric constants 2.5 or higher), in particular polyesters, polycarbonates (PCs), polystyrenes (PS), polymethyl methacrylates (PMMA). ), Polyamide, polyethylene, polypropylene, styrene / acrylonitrile (SAN) or acrylonitrile / butadiene / styrene (ABS). Polyester and polyamides are preferred. In particular, condensation products of linear aromatic polyesters or terephthalic acids with 1,4-bis (hydroxymethyl) cyclohexane obtainable by multicondensation of terephthalic acid and glycols (especially ethylene glycol), for example polyethylene terephthalate ( PET) or polybutylene terephthalate (PBTP); Polycarbonates such as polycarbonates formed from α, α-dimethyl-4,4'-dihydroxydiphenylmethane and phosgene; Or polyvinyl chloride or polyamide-based polymers, for example nylon 6 or nylon 6.6. Very particular preference is given to polyaromatic polyesters, for example polyesters formed from terephthalic acid and glycols (especially ethylene glycol) or condensation product plastics of terephthalic acid with 1,4-bis (hydroxymethyl) -cyclohexane .

Plastics are dyed, for example, by mixing the dye components of the tricolor mixture into these substrates using a roll mill or mixing or grinding apparatus to allow the dye to dissolve or finely disperse in the plastic. The plastic with the mixed dye is then processed by conventional methods, such as calendering, pressing, extrusion, spread coating, spinning, casting or injection molding so that the dyeing material obtains its ultimate form. The dye is also directly before the actual processing step, for example immediately before the simultaneous direct processing of, for example, continuous metered solid dyes, for example powder dyes and granulated or powdered plastics and also any further substances (eg additives) simultaneously. It may be added to the inlet of the extruder which is the mixing injection zone and mixed. In general, however, it is preferable to mix the dyes in advance in the plastics, since a more uniform dyeing substrate can be obtained.

The present invention further provides dyed or printed hydrophobic fibrous materials, preferably polyester fabrics and also bulk dyed plastics provided by the processes described above.

The following examples illustrate the invention. Unless stated otherwise, parts and percentages are by weight. The temperature is in degrees Celsius. Parts by weight are related to parts of capacity as grams are in cubic centimeters.

Example 1:

145.0 parts by weight of concentrated sulfuric acid and 70.0 parts by weight of chlorosulfonic acid are added to the reaction vessel. 36.0 parts by weight of the compound of formula 50 is added at 25 ° C. and the mixture is then stirred at 25-30 ° C. for 2 hours.

Formula 50

It is then placed on 1500 parts by weight of ice water and the precipitated product is suction filtered, neutral washed and dried.

This gives 32.0 parts by weight of the compound of formula 51.

Formula 51

17.0 parts by weight of the compound of formula 53 is introduced into 20 parts by weight of pyridine and 150 parts by weight of nitrobenzene, and the mixture is heated to 110 ° C. To 15 parts by weight of nitrobenzene, a 7.2 parts by weight solution of isobutyryl chloride is added dropwise at 110 ° C. over about 30 minutes. The mixture is then stirred for 2 hours. The reaction mixture is then cooled to 20-40 [deg.] C. and filtered directly or diluted with methanol and then the filter residue is washed with methanol and water and dried. This yields 18.0 parts by weight of a dye of formula (7) which dyes the polyester in a light red hue.

Formula 7

Example 2:

100 g of polyester fabric, at room temperature, with a solution ratio of 20: 1, 0.07 g of dye of formula 7, 0.058 g of dye of formula 2, 0.57 g of dye of formula 26, 1 g / l of ammonium sulfate and 0.5 g / l of commercially available leveling agent It was immersed in a solution containing and adjusted to a pH of 4.5 to 5 with 80% formic acid. The solution is then heated to 60 ° C. at a rate of 3 ° C. per minute and then to 130 ° C. at a rate of 2 ° C. per minute. The solution is kept at 140 ° C. for 60 minutes. The solution is then cooled to 40 ° C. and the dyed polyester fabric washed with water, and 5 g / l of 30% sodium hydroxide solution, 2 g / l of 85% sodium dithionite solution and 1 g / l of commercial detergent at 70-80 ° C. Reduction rinse for 20 minutes in the bath containing. The finished dyeings are then washed with water and dried. The dyeings obtained are beige and have good all-round fastness, in particular good light fastness.

Example 3:

100 g of polyester fabric, at room temperature with a solution ratio of 20: 1, 0.086 g of dye of formula 14, 0.181 g of dye of formula 2, 0.41 g of dye of formula 26, 1 g / l of ammonium sulfate and 0.5 g / l of commercially available leveling agent It was immersed in a solution containing and adjusted to a pH of 4.5 to 5 with 80% formic acid. The solution is then heated to 60 ° C. at a rate of 3 ° C. per minute and then to 130 ° C. at a rate of 2 ° C. per minute. The solution is kept at 140 ° C. for 60 minutes. The solution is then cooled to 40 ° C. and the dyed polyester fabric is washed with water and contains 5 ml / l 30% sodium hydroxide solution, 2 g / l 85% sodium dithionite solution and 1 g / l commercial detergent at 70-80 ° C. 20 minutes reduction cleaning in a bath. The finished dyeings are then washed with water and dried. The dyeings obtained are dark gray and have good all-round fastness, in particular good light fastness.

Example 4:

1200.00 g of polyester chips (PET Arnite D04-300, DSM) were pre-dried at 130 ° C. for 4 hours and then at a rate of 60 revolutions per minute for 15 minutes until homogeneous in a roller rack. Mix with g The homogeneous mixture is extruded with a twin screw 25 mm extruder (Collin, D 85560 Ebersberg) containing six heating zones at a maximum temperature of 275 ° C., quenched with water and a Turb Etuve TE 25 granulator (MAPAG AG, CH 3001 Bern) and then dried at 130 ° C. for 4 hours. A red polyester chip is obtained which has good universal fastness, in particular very good light fastness and hot light fastness.

Example 5:

Instead of the dye mixture, Example 2 is repeated using 0.7 g of the dye of formula (2). The dyeings obtained are blue and have good all-round fastness, especially good light fastness.

Claims (9)

delete delete Dyes of formula 7. Formula 7

The compound of formula 50 is cyclized in oleum / chlorosulfonic acid to obtain a compound of formula 51, and then reacted with a compound of formula (CH ₃ ) ₂ -CH-COCl to form a dye of formula 7. To prepare a dye of formula 7 according to claim 3. Formula 50

Formula 51

Tricolor dyeing or printing of the produced natural polymer and hydrophobic synthetic fibrous material, characterized by using at least one blue dye of formula 2 to 6 together with at least one red dye of formula 7 to 25 and yellow dye of formula 26 How to. Formula 2

Formula 3

Formula 4

Formula 5

Formula 6

Formula 7

Formula 8

Formula 9

Formula 10

Formula 11

Formula 12

Formula 13

Formula 14

Formula 15

Formula 16

Formula 17

Formula 18

Formula 19

Formula 20

Formula 21

Formula 22

Formula 23

Formula 24

Formula 25

Formula 26

A tricolor dye comprising at least one blue dye of formulas 2 to 6 as defined in claim 5 together with at least one red dye of formulas 7 to 25 as defined in claim 5 and a yellow dye of formula 26 as defined in claim 5 mixture. delete delete Tone-in-tone dyed plastic, characterized in that the same tricolor dye mixture according to claim 6 is used to mass dye the plastic material from the dye bath and to print or dye the produced natural polymer or synthetic fiber material. A process for the combination of a material with a natural polymer or synthetic fibrous material produced.